The present invention relates to novel fungicidal compositions comprising a 2-imidazolin-5-one derivative and an amino acid amide derivative, which are intended in particular for protecting crops. The invention also relates to a process for protecting crops against fungal diseases.
Compounds derived from 2-imidazolin-5-ones with fungicidal action are known, in particular from European patent application EP 551,048, these compounds making it possible to prevent the growth and development of phytopathogenic fungi which attack or are liable to attack crops.
International patent application WO 96/03044 also discloses a certain number of fungicidal compositions comprising a 2-imidazolin-5-one in combination with one or more fungicidal active materials.
Patent applications EP-A-0,775,696 and EP-A-0,472,966 present novel compounds for fungicidal use which have an amino acid amide structure.
However, it is always desirable to improve the products which can be used by growers in order to control fungal diseases of crops, and in particular mildews.
It is also always desirable to reduce the doses of chemical products spread into the environment to control fungal attacks on crops, in particular by reducing the application doses of the products.
Lastly, it is always desirable to increase the number of antifungal products available to growers in order for them to find, among these products, the one which is best suited to their specific use.
One aim of the invention is thus to provide a novel fungicidal composition which is useful for the problems outlined above.
Another aim of the invention is to propose a novel fungicidal composition which is useful in the preventive and curative treatment of fungal diseases, for example of Solanacea plants and of grapevine.
Another aim of the invention is to propose a novel fungicidal composition which is of improved efficacy against mildew and/or Septoria leaf blotch in Solanacea plants and grapevine.
Another aim of the invention is to propose a novel fungicidal composition which is of improved efficacy against mildew and/or oidium and/or botrytis in grapevine.
It has now been found that these aims may be achieved, partly or totally, by means of the fungicidal compositions according to the present invention.
The subject of the present invention is thus, firstly, fungicidal compositions comprising a compound (I) of formula: 
in which:
M represents an oxygen or sulfur atom;
n is an integer equal to 0 or 1;
Y is a fluorine or chlorine atom or a methyl radical;
and a compound of formula (II): 
in which:
R and Rxe2x80x2, which ate identical or different, are chosen, independently of each other, from a linear or branched alkyl radical containing from 1 to 6 carbon atoms,
A represents a group chosen from A1 and A2 which have the respective formulae: 
X represents the hydrogen atom, a halogen atom chosen from chlorine, fluorine, bromine and iodine, a linear or branched alkyl radical containing from 1 to 6 carbon atoms, or a linear or branched alkoxy radical containing from 1 to 6 carbon atoms, and
the asterisks represent asymmetric centers;
the compound (I)/compound (II) ratio being between 50 and 0.01, preferably between 10 and 0.01 and even more preferably between 5 and 0.5.
The preferred compounds of formula (II) for the fungicidal compositions according to the invention are such that the asymmetric carbon center of the amino acid gives it the L configuration.
It is clearly understood that all the possible configurations of compound (II), i.e. all the isomers formed by the various configurations of the two asymmetric carbons, are included in the field of the present invention.
It is clearly understood that said fungicidal compositions can include a single compound (I) or more than one such compound and/or a single compound (II) or ore than one such compound, as well as another fungicidal compound, depending on the use for which they are intended.
The compositions according to the invention are advantageous for controlling, in particular, mildew and Septoria leaf blotch in crops, such as cucumber or pea, for example, in Solanacea plants, such as potato or tomato, as well as for controlling mildew in grapevine.
The compositions according to the invention can also be used for controlling other phytopathogenic diseases of crops which are well known to The person skilled in the art who has at his or her disposal the compounds of formula (I) and of formula (II).
Compound (I) is known, in particular, from patent application EP-A-0,629,616.
Compound (II), when A represents the group A1, and its use as a fungicide are described in particular in European patent application EP-A-0,775,696.
Compound (II), when A represents the group A2, and its use as a fungicide are described in particular in European patent application EP-A-0,472,996.
The compound (I)/compound (II) ratio is defined as being the ratio of the weight of these 2 compounds. This is likewise the case for any ratio of 2 chemical compounds, mentioned hereinbelow in the present text, insofar as a definition different from this ratio is not expressly indicated.
These compositions generally appreciably improve the respective and isolated action of compound (I) and of compound (II) for a certain number of fungi that are particularly harmful in crops, in particular for Solanaceae, more particularly for mildew in Solanacea plants, while at the same time retaining an absence of phytotoxicity toward these crops. This therefore results in an improvement in the spectrum of activity and a possibility of decreasing the respective dose of each active material used, the latter quality being particularly advantageous for readily appreciated ecological reasons.
The fungicidal compositions according to the invention for which:
compound (I) is the compound of formula (I) in which M is a sulfur atom and n is equal to 0, also known as (4-S)-4-methyl-2-methylthio-4-phenyl-1-phenylamino-2-imidazolin-5-one, referred to hereinbelow as xe2x80x9cCompound Axe2x80x9d, and
compound (IIA) is the compound of formula (II) in which R represents the isopropyl radical, A represents the group (A1), X represents the fluorine atom placed in position 6 on the 2-benzothiazolyl radical, the amino acid has the L configuration and the asymmetric carbon borne by the 2-benzothiazolyl radical, the R configuration, also known as N1-[(R)-1-(6-fluoro-2-benzothiazolyl)ethyl]-N2-isopropoxycarbonyl-L-valinamide, referred to hereinbelow as xe2x80x9cCompound Bxe2x80x9d, or alternatively
compound (IIB) is the compound of formula (II) in which R represents the isopropyl radical, A represents the group (A2), X represents the methyl radical placed in position 4 on the phenyl radical, whether it is in the form of a racemate or mixtures of enantiomers and/or of diastereoisomers or in the form of a pure optical isomer, also known as isopropyl [2-methyl-1-(1-phenylethylcarbamoyl)-propyl]carbamate, referred to hereinbelow as xe2x80x9cCompound Cxe2x80x9d, are preferred.
A particularly advantageous form of compound (C) is the product commonly called Iprovalicarb.
In the compositions according to the invention, the compound (I)/compound (II) ratio is advantageously chosen so as to produce a synergistic effect. The term synergistic effect is understood to refer in particular to that defined by Colby S. R. in an article entitled xe2x80x9cCalculation of the synergistic and antagonistic responses of herbicide combinationsxe2x80x9d published in the journal Weeds, 1967, 15, p. 20-22. The latter article uses the formula:
E=X+Yxe2x88x92XY/100
in which E represents the expected percentage of inhibition of the disease for the combination of the two fungicides at defined doses (for example equal to x and y respectively), X is the percentage of inhibition observed for the disease by the compound (I) at a defined dose (equal to x), Y is the percentage of inhibition observed for the disease by the compound (II) at a defined dose (equal to y). When the percentage of inhibition observed for the combination is greater than E, there is a synergistic effect.
The term xe2x80x9csynergistic effectxe2x80x9d also means the effect defined by application of the Tammes method, xe2x80x9cIsoboles, a graphic representation of synergism in pesticidesxe2x80x9d Netherlands Journal of Plant Pathology, 70(1964), p. 73-80.
The compound (I)/compound (II) ratio ranges indicated above do not in any way limit the scope of the invention, but are, rather, mentioned as a guide, a person skilled in the art being entirely capable of carrying out additional tests to find other values of the ratio of doses of these two compounds, for which a synergistic effect is observed.
The compositions according to the invention, comprising compound (I) and compound (II), make it possible to observe entirely noteworthy synergistic properties.
According to one variant of the compositions according to the invention, the compound (I)/compound (II) ratio is advantageously between 10 and 0.01, preferably between 5 and 0.2.
In general, the compositions according to the invention have shown good results when the compound (I)/compound (II) ratio is between 5 and 1.
Another subject of the invention is compositions comprising one or more combinations according to the invention as described above.
The invention also comprises processes for treating plants against phytopathogenic diseases, characterized in that a combination of a compound of formula (I) and a compound of formula (II) is applied. It is also possible to apply a composition containing the two active materials, or, either simultaneously or successively so as to have the conjugated effect, two compositions each containing one of the two active materials.
These compositions cover not only compositions which are ready to be applied to the crop to be treated by means of a suitable device, such as a spraying device, but also commercial concentrated compositions which need to be diluted before they are applied onto the crop.
The present invention provides a method for controlling a large variety of phytopathogenic diseases of crops, in particular for controlling Septoria leaf blotch and mildew. These diseases can be controlled by direct application to the leaves.
The present invention thus provides a process for curatively or preventively controlling the phytopathogenic diseases of crops, which comprises treatment of said crop (for example by application or by administration) with an effective and non-phytotoxic amount of a combination as defined above. The expression xe2x80x9ctreatment of the cropxe2x80x9d means an application or administration of a fungicidal composition as described above onto the aerial parts of the crops or onto the soil in which they are growing and which are infested or liable to become infested with a phytopathogenic disease, such as mildew or Septoria leaf blotch, for example. The expression xe2x80x9ctreatment of the cropxe2x80x9d also means treatment of the reproduction products of the crop, such as the seeds or the tubers, for example.
The compositions described below are used in general for application onto growing vegetation, or onto areas in which crops are grown, or for the coating of or film-forming on the seeds.
Among the means which are suitable for applying the compounds of the invention, mention may be made of the use of powders, foliar sprays, granules, mists or foams, or alternatively means in the form of suspensions of finely divided or encapsulated compositions; for the treatment of soils or roots with liquid imbibitions, powders, granules, fumes or foams; for application onto the plant seeds, the use, as agents for forming a film on or coating seeds, of powders or liquid broths.
The compounds or compositions according to the invention are, appropriately, applied to the vegetation and in particular to the leaves infested with the phytopathogenic fungi. Another method for applying the compounds or compositions according to the invention is to add a formulation containing the active material, with the irrigation water. This irrigation can be an irrigation using sprinklers.
The formulations which are suitable for the applications of the compositions according to the invention comprise formulations which are suitable for use in the form, for example, of sprays, powders, granules, mists, foams, emulsions or the like.
In practice, for controlling the phytopathogenic diseases of crops, one method, for example, consists in applying an effective amount of a composition according to the invention onto the plants or onto the medium in which they are growing. For such a method, the active material is generally applied onto the same area in which the infestation needs to be controlled, at an effective dose of between about 5 g and about 2 kg of active material per hectare of area treated. Under ideal conditions, depending on the nature of the phytopathogenic fungus to be treated, a lower dose may offer adequate protection. Conversely, poor climatic conditions, resistance or other factors may require higher doses of active material. The optimum dose usually depends on several factors, for example on the type of phytopathogenic fungus to be treated, on the type or level of development of the infested plant, on the density of vegetation, or alternatively on the method of application. More preferably, an effective dose of active material is between about 20 g/ha and about 1000 g/ha.
For their use in practice, the compositions according to the invention can be used alone and can also advantageously be used in compositions containing one or other of the active materials or alternatively both of them together, in combination or association with one or more other compatible components which are, for example, solid or liquid fillers or diluents, adjuvants, surfactants or equivalents, which are suitable for the desired use and which are acceptable for uses in agriculture. The compositions can be of any type known in the sector which are suitable for application onto all types of plantations or crops. These compositions, which can be prepared in any manner known in this sector, also form part of the invention.
The compositions can also contain ingredients of other types, such as protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, oils for spraying, stabilizers, preserving agents (in particular moldproofing agents), sequestering agents or the like, as well as other known active ingredients which have pesticidal properties (in particular fungicidal, insecticidal, acaricidal or nematicidal properties) or which have properties of regulating plant growth. More generally, the compounds used in the invention can be combined with any solid or liquid additives corresponding to the usual formulation techniques.
The effective working doses of the combinations used in the invention can vary within wide proportions, in particular depending on the nature of the phytopathogenic fungi to be eliminated or the degree of infestation, for example, of the plants with these fungi.
In general, the compositions according to the invention usually contain from about 0.05% to about 99% (by weight) of one or more compositions according to the invention, from about 1% to about 95% of one or more solid or liquid fillers and, optionally, from about 0.1% to about 50% of one or more other compatible compounds, such as surfactants or the like.
In the present account, the term xe2x80x9cfillerxe2x80x9d means an organic or inorganic, natural or synthetic component with which the active component is combined to facilitate its application, for example, onto the plants, the seeds or the soil. This filler is consequently generally inert and it must be acceptable (for example acceptable for agronomic uses, in particular for treating plants).
The filler can be solid, for example clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers (for example ammonium salts), natural soil minerals, such as kaolins, clays, talc, lime, quartz, attapulgite, montmorillonite, bentonite or diatomaceous earths, or synthetic minerals, such as silica, alumina or silicates, in particular aluminum or magnesium silicates. The solid, fillers which are suitable for granules are as follows: natural, crushed or broken rocks, such as calcite, marble, pumice, sepiolite or dolomite; synthetic granules of inorganic or organic flours; granules of organic material such as sawdust, coconut shell, corn ear or envelope, or tobacco stem; kieselguhr, tricalcium phosphate, powdered cork or adsorbent carbon black; water-soluble polymers, resins, waxes; or solid fertilizers. Such compositions can, if so desired, contain one or more compatible agents such as wetting agents, dispersing agents, emulsifiers or dyes which, when they are solid, can also act as diluents.
The fillers can also be liquid, for example: water, alcohols, in particular butanol or glycol, as well as ethers or esters thereof, in particular methyl glycol acetate; ketones, in particular acetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone or isophorone; petroleum fractions such as paraffinic or aromatic hydrocarbons, in particular xylenes or alkylnaphthalenes; mineral or plant oils; aliphatic chlorohydrocarbons, in particular trichloroethane or methylene chloride; aromatic chlorohydrocarbons, in particular chlorobenzenes; water-soluble or highly polar solvents such as dimethylformamide, dimethyl sulfoxide, N,N-dimethyl-acetamide or N-methylpyrrolidone; N-octylpyrrolidone, liquefied gases; or the like, whether they are taken separately or as a mixture.
The surfactant can be an emulsifier, a dispersing agent or a wetting agent, of ionic or nonionic type or a mixture of these surfactants. Among those surfactants which are used, for example, are polyacrylic acid salts, lignosulfonic acid salts, phenolsulfonic or naphthalenesulfonic acid salts, polycondensates of ethylene oxide with fatty alcohols or fatty acids or fatty esters or fatty amines, substituted phenols (in particular alkylphenols or arylphenols) ester-salts of sulfosuccinic acid, taurine derivatives (in particular alkyl taurates), phosphoric esters of alcohols or of polycondensates of ethylene oxide with phenols, fatty acid esters with polyols, or sulfate, sulfonate or phosphate functional derivatives of the compounds described above. The presence of at least one surfactant is generally essential when the active material and/or the inert filler are insoluble or only sparingly soluble in water and when the filler for said composition to be applied is water.
The compositions according to the invention can also contain other additives such as adhesives or dyes. Adhesives such as carboxymethylcellulose, or natural or synthetic polymers in the form of powders, granules or matrices, such as gum arabic, latex, polyvinylpyrrolidone, polyvinyl alcohol or polyvinyl acetate, natural phospholipids, such as cephalins or lecithins, or synthetic phospholipids can be used in the formulations. It is possible to use dyes such as inorganic pigments, such as, for example: iron oxides, titanium oxides, Prussian blue; organic dyestuffs, such as those of the alizarin, azo or metal phchalocyanin type; or of trace elements such as iron, manganese, boron, copper, cobalt, molybdenum or zinc salts.
The compositions containing the combinations of the invention, which are used to control the phytopathogenic fungi of crops, can also contain stabilizers, other fungicidal agents, insecticides, acaricides, nematicides, anti-helminths or anti-coccidoses, bactericides, attractant or repellent agents or pheromones for arthropods or vertebrates, deodorizers, flavorings or dyes.
These stabilizers can be chosen for the purpose of improving the strength, the persistence, the safety, the spectrum of action on the phytopathogenic fungi of crops or to make the composition capable Of accomplishing other useful functions for the areas treated.
By way of example, the compositions according to the invention may contain, in addition to a compound of formula (I) and a compound of formula (II), another active material possessing fungicidal properties.
Appropriately, the other fungicidal active material may be iprodione. Other fungicidal active materials may however be completely suitable without departing from the subject of the present invention.
Thus, when the other active material is iprodione, compositions which are completely appropriate are for example those containing compound (A), compound (B) and iprodione, or alternatively compound (A), compound (C) and iprodione.
For their use in agriculture, the combinations according to the invention are consequently in the form of compositions which are in a variety of solid or liquid forms.
The solid forms of the compositions which can be used are pulverulent powders (with an amount of active material, combination according to the invention, ranging up to 99%), wettable powders or granules (including water-dispersible granules), and in particular those obtained by extrusion, compacting, impregnation on a filler or by granulation using a powder (the amount of active material, combination according to the invention, in these wettable granules or powders, being between about 0.5% and about 99%). The homogeneous or heterogeneous solid-compositions containing a composition according to the invention, for example the granules, pellets, briquettes or capsules, can be used for treating stagnant or trickling waters over a relatively long period of time.
A similar effect can be obtained by using intermittent feeds or seepages of the water-dispersible concentrates as described later.
The liquid compositions comprise, for example, aqueous or non-aqueous solutions or suspensions (such as emulsifiable concentrates, emulsions, flowables, dispersions or solutions) or alternatively aerosols. The liquid compositions also comprise, in particular, emulsifiable concentrates, dispersions, emulsions, gels, fiowables, aerosols, wettable powders (or powders for spraying) dry flowables or dry pastes as liquid comDosition forms or as forms intended to form liquid compositions when they are applied, such as, for example, aqueous sprays (including those of low or ultra-low volume) or mists or aerosols.
The liquid compositions, for example in the form of soluble or emulsifiable concentrates, usuallv comprise from about 5 to about 95% by weight of active material, whereas the ready-to-use emulsions or solutions themselves contain from about 0.01 to 20% of active material. In addition to the solvent, the soluble or emulsifiable concentrates can contain, wnen necessary, from about 2 to about 50% of suitable additives, such as stabilizers, surfactants, penetrating agents, corrosion inhibitors, dyes or adhesives. Irrespective of their concentrations, the emulsions, which are particularly suitable for application onto plants, for example, can be obtained from these concentrates by dilution with water. These compositions are included in the field of compositions which can be used in the present invention. The emulsions can cover the forms of water-in-oil or oil-in-water type and they can be of tnick consistency or even in gel form.
All these aqueous dispersions or emulsions or mixtures for spraying can be applied, for example, to vegetation by any suitable means, firstly by spraying, at doses which are generally from about 100 to about 1200 liters of mixture to be sprayed per hectare, but can be higher or lower (for example of low or ultra-low volume), depending on the need or the application technique.
The concentrated suspensions, which can be applied by spraying, are prepared so as to be in the form of a fluid, stable product which does not sediment (in the case of fine grains), generally containing from about 10 to about 75% by weight of active material, from about 0.5 to about 30% of surfactants, from about 0.1 to about 10% of Theological agents, from about 0 to about 30% of suitable additives, such as antifoaming agents, corrosion inhibitors, stabilizers, penetrating agents, adhesives and, as filler, water or an organic liquid in which, the active material is insoluble or only sparingly soluble. Organic solids or inorganic salts can be dissolved in the filler in order to prevent any setting to a solid or to act as antifreeze for the water.
The wettable powders or soluble powders (powder for spraying) are generally prepared so as to contain from about 10 to about 100% by weight of active material, from about 0 to about 90% of solid filler, from about 0 to about 5% of a wetting agent, from about 0 to about 10% of a dispersant and, when necessary, from about 0 to about 80% of one or more stabilizers and/or other additives, such as penetrating agents, adhesives, anti-caking agents, dyes and the like. In order to obtain these wettable powders, the active material(s) is (are) intimately mixed in a suitable mixer with other additional substances which can be impregnated onto a porous support and is (are) ground in a mill or other suitable device designed for this purpose. This gives wettable powders whose wettabilily and suspension quality are very advantageous. They can be in suspension in water to give any type of concentration desired and this suspension can advantageously be used in particular for application to the leaves of plants.
The xe2x80x9cwater-dispersible granulesxe2x80x9d (WG) and the soluble granules (SG) have compositions which are substantially similar to those of the wettable powders. They can be prepared by granulation of the formulations described for the wettable powders, either according to a so-called wet-route process (by means of contact between the finely ground active material with the inert filler and a small amount of water, for example 1 to 20% by weight, or with an aqueous solution of a binder or a dispersing agent, followed by drying and screening), or according to a so-called dry-route process (grinding followed by compacting and screening) like those obtained by extrusion.
The doses and concentrations of the compositions formulated can vary depending on the method of application or the nature of the compositions or depending on their use. In general, the formulated compositions usually contain from about 0.00001% to about 100%, more particularly from about 0.0005% to about 80%, by weight of at least one combination according to the invention, or of all of the active materials (i.e. a composition of the invention as a mixture with other pesticidal substances or stabilizers). In concrete terms, the compositions used and their working doses will be chosen so as to obtain the effect(s) desired by the farmer, horticulturalist, forester, any technical staff responsible for controlling the phytopathogenic fungi of crops or any other person qualified in this field.